EP0686664A1 - Propylenpolymerzusammensetzung, Verfahren zu seiner Herstellung und Verwendung - Google Patents

Propylenpolymerzusammensetzung, Verfahren zu seiner Herstellung und Verwendung Download PDF

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Publication number
EP0686664A1
EP0686664A1 EP95201399A EP95201399A EP0686664A1 EP 0686664 A1 EP0686664 A1 EP 0686664A1 EP 95201399 A EP95201399 A EP 95201399A EP 95201399 A EP95201399 A EP 95201399A EP 0686664 A1 EP0686664 A1 EP 0686664A1
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EP
European Patent Office
Prior art keywords
weight
composition according
propylene
polymer
chosen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP95201399A
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English (en)
French (fr)
Inventor
Morand Lambla
Didier Graebling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay Polyolefins Europe Belgium SA
Solvay SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Polyolefins Europe Belgium SA, Solvay SA filed Critical Solvay Polyolefins Europe Belgium SA
Publication of EP0686664A1 publication Critical patent/EP0686664A1/de
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to a composition based on propylene polymer with modified rheological properties. It also relates to a process for obtaining this composition as well as its use for the shaping of objects by the processes of extrusion, calendering, injection and thermoforming as well as for the manufacture of foams. Finally, it relates to artifacts containing this composition.
  • the crystalline polymers of propylene are known for their mechanical properties as well as for their transparency and their resistance to heat. Their relatively low cost makes them a material of choice for a large number of applications such as the formation of shaped objects.
  • crosslinking agent is an acrylate
  • the rheological properties of these mixtures remain insufficient for certain applications such as thermoforming and the manufacture of foams.
  • patent application JP-A-59/223740 discloses in full generality of the polypropylene-based compositions having both good impact resistance and a high crystallization speed obtained by melt blending of polypropylene and polyethylene in the presence of an ethylene-propylene copolymer having an isotacticity measured by nuclear magnetic resonance 13C less than 0.7, an organic peroxide and a crosslinking agent similar to that described in document JP-A-59/093711.
  • compositions belonging to the prior art have improved rheological properties in the molten state and in particular an increase in the resistance to deformation during elongation or extension and which does not have the drawbacks.
  • Polymer (a) is chosen from homopolymers of propylene and copolymers of the latter containing at least 50 mol% of propylene and at least one other monomer chosen from ⁇ -olefins containing from 2 to 20 carbon atoms, unsaturated organic acids and their derivatives, vinyl esters, aromatic vinyl compounds , vinylsilanes as well as unconjugated aliphatic and monocyclic diolefins, alicyclic diolefins having an endocyclic bridge and conjugated aliphatic diolefins.
  • ⁇ -olefins examples include ethylene, 1-butene, 1-pentene, 1-hexene, methyl-1-butenes, methyl-1-pentenes, 1- octene and 1-decene.
  • acrylic acid methacrylic acid, maleic acid, methyl methacrylate, glycidyl acrylate and methacrylate, maleic anhydride, acetate and butyrate vinyl, styrene and methylstyrene, vinyltrimethylmethoxysilane and ⁇ -methacryloyloxypropyltrimethoxysilane as well as 1,4-hexadiene, 4-vinylcyclohexene, dicyclopentadiene, methylene- and ethylidenenorbornene, butadiene.
  • Copolymers of propylene with ⁇ -olefins are particularly preferred and among these copolymers of propylene with at least one other monomer chosen from ethylene and 1-butene give good results.
  • copolymers of propylene means both random copolymers of propylene and block copolymers of the latter.
  • the former are generally made up of macromolecular chains in which the monomers are statistically distributed.
  • the propylene content of these random copolymers is most often greater than 70% by mole, preferably greater than or equal to 75% by mole.
  • the second consist of separate blocks of variable composition; each block consisting of a homopolymer of propylene or of another ⁇ -olefin or of a random copolymer comprising propylene and at least one other monomer chosen from the monomers mentioned above.
  • Block copolymers of propylene are generally obtained by polymerization in several consecutive stages in which one prepares successively the different blocks.
  • Propylene copolymers are generally preferred. Block copolymers of propylene give good results.
  • Block copolymers which contain 30 to 90% by weight of a first block which is a homopolymer of propylene and 70 to 10% by weight of a second block which is a random copolymer of propylene containing from 40 to 60% in moles of ethylene give particularly good results.
  • the polymer (b) is chosen from homopolymers of ethylene and copolymers of ethylene containing at least 90 mol% of ethylene and at least one other monomer chosen from ⁇ -olefins containing from 3 to 20 carbon atoms as well than the other monomers described above in connection with the polymer (a).
  • this other monomer is chosen from ⁇ -olefins and diolefins.
  • 1-butene and 1-hexene are well suited.
  • the amount of ethylene in the polyethylene (b) is most often greater than or equal to 95% by mole. Polymers containing at least 97 mol% of ethylene are particularly suitable.
  • the preferred ethylene polymers (b) most often have a density greater than 0.92 and more particularly from 0.94 to 0.98.
  • Polymers (a) and (b) are well known to those skilled in the art. They are generally obtained by polymerization of the monomers in one or more stages in the presence of catalysts of the Ziegler Natta type or of catalysts based on chromium.
  • the amount of polymer (b) used is generally greater than or equal to 5% by weight, and preferably greater than or equal to 10% by weight.
  • the polymer (a) is a propylene homopolymer, it is found that this quantity is advantageously at least 20% by weight. In this particular case, the amount of polymer (b) is most often less than 40% by weight.
  • the amount of polymer (b) used is also advantageously less than or equal to 30% by weight, more particularly less than or equal to 20% by weight. In this case, good results are obtained when the amount of polymer (b) is 10 to 20% in weight.
  • the functional compounds (c) which can be used in the compositions according to the present invention generally contain at most 7 acrylate groups.
  • Compounds (c) which contain 3 to 5 acrylate groups give good results.
  • these compounds mention may be made of the following compounds commonly known as trimethylol - propane - triacrylate, trimethylol - propane - ethoxy - triacrylate, glycerol - propoxy - triacrylate, pentaerythritol - triacrylate, di - trimethylol - propane - tetracrylate, pentaerythritol - tetracrylate, pentaerythritol - ethoxy - tetracrylate, trimethylol - propane - trimethacrylate and pentaerythritol - ethoxy - triacrylate. It goes without saying that one or more compounds (c) can be used.
  • trimethylol - propane - triacrylate trimethylol - propane - ethoxy - triacrylate
  • pentaerythritol - triacrylate di - trimethylol - propane - tetracrylate
  • pentaerythritol - ethoxy - tetracrylate give particularly good results.
  • the amount of functional compound (c) is most often at least 0.05% by weight, preferably at least 0.5% by weight. Good results are obtained when the amount of functional compound is less than or equal to 6% by weight, more particularly less than or equal to 2% by weight. Amounts of 0.5 to 2% by weight give particularly good results.
  • the compound (d) capable of generating free radicals is most often chosen from organic peroxides, persulfates and diazo compounds.
  • organic peroxides persulfates and diazo compounds.
  • these compounds include N-bromosuccinimide, benzoyl and dicumyl peroxides, cumene hydroperoxide, 2,5 - dimethyl - 2,5 - ditertiobutylperoxyhexane, potassium persulfates or d ammonium, azobisisobutyronitrile, etc.
  • the most suitable compounds are those which decompose at the temperatures at which the mixture is melted.
  • Peroxides are generally preferred. Among these 2,5 - dimethyl - 2,5 - ditertiobutylperoxyhexane, tertbutylcumyl peroxide and dicumyl peroxide give good results.
  • the amount of compound (d) used is most often greater or equal to 0.01% by weight. It is also generally less than or equal to 1% by weight, more particularly less than or equal to 0.1% by weight. Amounts of 0.01 to 0.1% by weight give good results.
  • compositions according to the present invention are obtained by melt mixing the various components. Most often this melt-mixing is carried out under conditions such that there is at least partial reaction of the molecules of the functional compound (c) with one another and / or with the polymers (a) and / or (b).
  • the conditions under which this mixing is carried out are not critical insofar as they induce the at least partial melting of the polymers (a) and (b). Preferably, they are such that there is complete melting of the polymers (a) and (b).
  • the mixing is carried out at a temperature not exceeding 400 ° C, preferably not 300 ° C and more particularly not 250 ° C.
  • the minimum temperature at which the melt mixing is carried out is greater than or equal to 130 ° C., preferably greater than or equal to 150 ° C. and more particularly greater than 180 ° C. Very good results are obtained when this temperature is greater than 180 ° C. and less than or equal to 230 ° C.
  • the duration of the mixing is chosen taking into account the nature of the compounds used and the mixing temperature. This duration generally varies from 5 seconds to 120 minutes, most often from 10 seconds to 30 minutes.
  • the mixing of the polymers (a) and (b) with the compounds (c) and (d) is carried out in any device known for this purpose. So you can use internal or external mixers. Internal mixers are the most suitable and among them discontinuous mixers of the BRABENDER type and continuous mixers such as extruders.
  • Extruders are generally preferred.
  • the order of introduction of the various components into the mixer is not critical. It is equally possible to introduce them in isolation and successively or to carry out a premix of the various constituents with each other or of only a part of these constituents.
  • the polymer (a) is a propylene homopolymer
  • the premix is then subjected to a melt mixture with the compounds (c) and (d) to obtain the compositions according to the invention.
  • compositions according to the present invention can also contain other conventional additives such as for example stabilizers, lubricants, antistatic agents, nucleating agents, foaming agents, glass fibers or any other filler.
  • additives such as for example stabilizers, lubricants, antistatic agents, nucleating agents, foaming agents, glass fibers or any other filler.
  • compositions according to the invention are obtained in the absence of an elastomer separate from the polymers (a) and (b).
  • the preferred compositions are obtained under conditions such that the polymers (a) and (b) constitute at least 99% by weight of the whole of the polymers used.
  • the compositions having the best performance are obtained by using as polymers only polymers (a) and (b).
  • compositions according to the present invention exhibit particularly advantageous rheological and viscoelastic properties. It is found in fact that they have in the molten state, an increase in the resistance to deformation during elongation or extension. Such a phenomenon is generally called "structural hardening under stress". It can easily be characterized by determining, for a given temperature and speed of elongation, the variation in the elongational viscosity of the composition in the molten state as a function of the elongation time. Subjected to such tests, the compositions according to the present invention exhibit an increase in elongational viscosity until the rupture of the melt.
  • compositions according to the present invention particularly advantageous for obtaining shaped objects by injection and by extrusion and in particular by extrusion- or injection-blowing, thermoforming or coating (see for example ANTEC 92/569). Such a property is also essential for the manufacture of foams.
  • Such uses of the compositions according to the invention as well as the shaped articles containing said compositions therefore constitute additional aspects of the present invention.
  • the dispersion of the polymers (a) and (b) in the compositions according to the invention is remarkably fine, homogeneous and stable, that is to say that it is preserved in the melt in the absence of shearing or kneading.
  • Such a property makes it possible to use the compositions according to the invention many times without observing significant decreases in their performance, which facilitates recycling.
  • compositions according to the present invention contain little and advantageously no agglomerates of higher viscosity (hereinafter called gels) capable of altering the shaped objects containing them.
  • the method according to the present invention has the advantage of being particularly simple to implement. It also makes it possible to obtain, in a reproducible manner and in relatively short periods of time, the compositions according to the invention.
  • compositions according to the invention are obtained using a corotative twin-screw extruder of the WERNER & PFLEIDERER ZSK 3O type, the screws of which successively consist of feeding, mixing and devolatilization zones.
  • the temperature of the feed zone is 160 ° C at the inlet and 180 ° C at the outlet; the temperature of the mixing zone is 190 ° C. at the inlet and 210 ° C. at the outlet, the temperature of the devolatilization zone is 210 ° C.
  • the screw rotation speed is 150 revolutions / min for a material flow of 5 kg / h.
  • the different products are premixed in a barrel.
  • the elongational viscosity of the compositions obtained in the examples is determined using a rheometer sold by RHEOMETRICS under the name RHEOMETRICS EXTENSIONAL RHEOMETER RER-9000.
  • the curves shown in Figures 1 and 2 appended hereto show the variation, at 190 ° C, of the elongational viscosity in the molten state (expressed in Pa.s) as a function of time ( expressed in s) for an elongation gradient (expressed in s ⁇ 1) of 0.1 for examples 1 to 4, 8, 9, 2R, 6R and 7R and 0.3 for example 5R.
  • curve 1 corresponds to example 1
  • curve 4 to example 4 curve 5 to example 5R and curve 6 in Example 6R
  • curve 1 corresponds to example 7R, curve 2 to example 8 and curve 3 to example 9.
  • the determination of the gel content of the compositions is carried out with a mixture of xylene isomers (boiling point between 137 and 140 ° C.) using a Soxhlet type extractor. The extraction is continued for 35 hours.
  • composition thus obtained is free from gels.
  • the extruder is fed with the mixture of polymers of Example 1 but without the addition of TMPTA or DHBP.
  • the RER diagram of this composition represented by curve 2 of FIG. 1 shows the absence of hardening under stress. In fact the elongational viscosity decreases until the ductile rupture of the sample.
  • the extruder is fed with the same mixture as that of Example 1 except that the propylene block copolymer is replaced by a random propylene copolymer sold under the name ELTEX P KF 001 P by SOLVAY.
  • the RER diagram of the composition thus obtained represented in curve 3 (FIG. 1) shows the same phenomenon of hardening under stress as that manifested by the composition of Example 1. This composition is free from gels.
  • Example 3 is reproduced, except that the TMPTA is replaced by trimethylol-propane-ethoxy-triacrylate.
  • the extruder is fed with the mixture of polymers of Example 3 but without the addition of TMPTA or DHBP.
  • the RER diagram of this composition (curve 5, FIG. 1) shows the same phenomenon as that of the composition of example 2R.
  • Example 1 is reproduced but omitting the polyethylene and putting using 3,000 g of a homopolymer sold under the name ELTEX P HL 001 P by SOLVAY.
  • the RER diagram of the composition thus obtained (curve 6, FIG. 1) does not show the phenomenon of hardening under stress.
  • Example 1 is reproduced, except that the TMPTA is replaced by an equivalent amount of triethylene glycol dimethacrylate (TEGDMA).
  • TEGDMA triethylene glycol dimethacrylate
  • Example 1 is reproduced, except that the TMPTA is replaced by an equivalent amount of trimethylol-propane-trimethacrylate (TRIM).
  • TMPTA trimethylol-propane-trimethacrylate
  • the RER diagram shown in curve 2 of FIG. 2 shows the phenomenon of structural hardening under stress.
  • a melt premix is carried out by feeding the extruder with a mixture containing 2400 g of a propylene homopolymer sold under the name ELTEX P HL 402 and 600 g of polyethylene ELTEX A 1050 P.
  • the speed of rotation of the screw of the extruder is 100 rpm and the material flow rate is 4 kg / h.
  • Example 1 is then reproduced by feeding the extruder with this mixture and 0.6 g / kg of DHBP and 12 g / kg of TMPTA.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
EP95201399A 1994-06-06 1995-05-30 Propylenpolymerzusammensetzung, Verfahren zu seiner Herstellung und Verwendung Ceased EP0686664A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9400558A BE1008432A3 (fr) 1994-06-06 1994-06-06 Composition a base de polymere du propylene, procede pour son obtention et utilisation.
BE9400558 1994-06-06

Publications (1)

Publication Number Publication Date
EP0686664A1 true EP0686664A1 (de) 1995-12-13

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EP95201399A Ceased EP0686664A1 (de) 1994-06-06 1995-05-30 Propylenpolymerzusammensetzung, Verfahren zu seiner Herstellung und Verwendung

Country Status (6)

Country Link
US (1) US5569717A (de)
EP (1) EP0686664A1 (de)
JP (1) JPH08311269A (de)
KR (1) KR960001003A (de)
CN (1) CN1078601C (de)
BE (1) BE1008432A3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0884355A1 (de) * 1997-06-10 1998-12-16 PCD Polymere AG Feinzellige Polyolefinschaumstoffe

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19646118A1 (de) * 1996-11-08 1998-05-14 Basf Ag Mit ungesättigten Estern teilvernetzte Kunststoffmassen
US20030051992A1 (en) * 2000-05-16 2003-03-20 Earthfirst Technologies, Inc. Synthetic combustible gas generation apparatus and method
EP1195416A3 (de) * 2000-10-05 2005-12-28 Degussa AG Polymerisierbare siliciumorganische Nanokapseln
US6646056B2 (en) * 2001-10-16 2003-11-11 Solvay Engineered Polymers Thermoplastic elastomer compositions
EP1357136A1 (de) * 2002-04-26 2003-10-29 ATOFINA Research Gegenstand aus Poylethylene mit hoher Dichte hergestellt durch Spritzgiessverfahren
CN100569818C (zh) * 2008-03-06 2009-12-16 中国科学院长春应用化学研究所 一种提高聚丙烯熔体强度的方法
CN101376683B (zh) * 2008-10-07 2011-09-21 中国科学院长春应用化学研究所 一种高熔体强度聚丙烯的制备方法
CN102558449A (zh) * 2011-12-13 2012-07-11 金发科技股份有限公司 一种高熔体强度的聚丙烯材料及其制备方法与应用

Citations (6)

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Publication number Priority date Publication date Assignee Title
EP0073435A2 (de) * 1981-08-21 1983-03-09 Luperox GmbH Verfahren zur Vernetzung und gegebenenfalls Verschäumung von Polypropylen
JPS5993711A (ja) 1982-11-22 1984-05-30 Mitsui Petrochem Ind Ltd 結晶性ポリプロピレンの改質方法
JPS59223740A (ja) 1983-06-02 1984-12-15 Mitsui Petrochem Ind Ltd ポリプロピレン組成物の製造方法
JPS60188412A (ja) * 1984-03-09 1985-09-25 Chisso Corp ポリオレフイン樹脂組成物の製造方法
EP0191990A2 (de) * 1984-12-27 1986-08-27 Nippon Oil Co. Ltd. Vernetzte Kunststoffzusammensetzungen
EP0520773A2 (de) * 1991-06-27 1992-12-30 Sekisui Chemical Co., Ltd. Schaumfähige Polyolefinzusammensetzungen

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US4424293A (en) * 1980-02-25 1984-01-03 The Furukawa Electric Co., Ltd. Crosslinkable polypropylene composition
KR920003034B1 (ko) * 1988-06-21 1992-04-13 동양나이론 주식회사 열가소성 탄성중합체 수지조성물 및 그 제조방법
ES2136671T3 (es) * 1993-03-18 1999-12-01 Basf Ag Copolimeros de propileno injertados con iniciadores, que se descomponen en radicales.

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
EP0073435A2 (de) * 1981-08-21 1983-03-09 Luperox GmbH Verfahren zur Vernetzung und gegebenenfalls Verschäumung von Polypropylen
JPS5993711A (ja) 1982-11-22 1984-05-30 Mitsui Petrochem Ind Ltd 結晶性ポリプロピレンの改質方法
JPS59223740A (ja) 1983-06-02 1984-12-15 Mitsui Petrochem Ind Ltd ポリプロピレン組成物の製造方法
JPS60188412A (ja) * 1984-03-09 1985-09-25 Chisso Corp ポリオレフイン樹脂組成物の製造方法
EP0191990A2 (de) * 1984-12-27 1986-08-27 Nippon Oil Co. Ltd. Vernetzte Kunststoffzusammensetzungen
EP0520773A2 (de) * 1991-06-27 1992-12-30 Sekisui Chemical Co., Ltd. Schaumfähige Polyolefinzusammensetzungen

Non-Patent Citations (2)

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Title
DATABASE WPI Derwent World Patents Index; AN 85-028507 *
DATABASE WPI Derwent World Patents Index; AN 85-279243 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0884355A1 (de) * 1997-06-10 1998-12-16 PCD Polymere AG Feinzellige Polyolefinschaumstoffe

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BE1008432A3 (fr) 1996-05-07
KR960001003A (ko) 1996-01-25
US5569717A (en) 1996-10-29
JPH08311269A (ja) 1996-11-26
CN1078601C (zh) 2002-01-30
CN1117505A (zh) 1996-02-28

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